CN102604039A - Preparation method of waterborne polyurethane material with resistance to yellowing - Google Patents
Preparation method of waterborne polyurethane material with resistance to yellowing Download PDFInfo
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Abstract
The invention relates to a preparation method of a waterborne polyurethane composite material with high resistance to yellowing. The preparation method comprises the following steps of: well dispersing nano-TiO2 in DMF (dimethylformamide) in a way of adding a dispersant; compounding MDI (diphenyl-methane-diisocyanate) with IPDI (isophorone diisocyanate), and reacting with polycarbonate diol to reduce the reaction degree of the MDI so as to get a waterborne polyurethane emulsion with higher stability; and adding nano-powder TiO2 into the polyurethane emulsion before emulsification, improving the dispersion stability of the nano-powder TiO2 in polyurethane, and adding an antioxidant 1010 and an ultraviolet absorbent UV-327 into the waterborne polyurethane emulsion to achieve better resistance to yellowing, wherein the yellowing grade is improved by 1-1.5 grades.
Description
Technical field
The present invention relates to a kind of preparation method of stain resistant aqueous polyurethane material.
Background technology
Designability and cutting property based on molecule; Polyurethane material is a kind of at the polymer materials that all has the broad scope of application aspect physicals and the chemical property, therefore is widely used in tackiness agent, coating, synthetic leather, material of construction and the automatic industrial.Aqueous polyurethane has overcome the with serious pollution shortcoming of solvent borne polyurethane, is dispersion medium with water, has characteristics such as nontoxic, energy-conservation, safe and reliable, and research initially promptly is widely used in the hide finishes.
Though aromatic waterborne polyurethane has mechanical property preferably when being used for hide finishes since structure contain be prone to color development the conjugation group, xanthochromia very easily when being used for white and light color leather is so limited its application.
Usually adopt modes such as adding UV light absorber (benzotriazole category, triazines), hindered amine as light stabilizer and oxidation inhibitor to improve the yellowing resistance of aromatic waterborne polyurethane in the industrial production.But because additive and the compatibility problem of polymkeric substance and the ageing problem of additive etc. make anti-xanthochromia effect be difficult to lastingly.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of stain resistant aqueous polyurethane material; The suitable finish of anti-xanthochromia that uses as white and light color leather of the water-base polyurethane material that obtains is to improve the xanthochromia grade and the nano-TiO of leather coating
2Dispersion stabilization in polyaminoester emulsion, the difficulty of reduction aromatic waterborne polyurethane building-up process.
Technical scheme of the present invention is following:
(1), preparation nano-TiO
2Dispersion liquid: in container, add dispersion agent and N respectively, dinethylformamide, and dispersion agent is dissolved fully, add nano-powder TiO then
2, in ultrasonic cell disruptor, sonicated 30min obtains nano-TiO under the 540w
2Dispersion liquid is subsequent use;
Wherein every 100mlN adds nano-powder TiO in the dinethylformamide
25 ~ 10g, dispersion agent 1.5 ~ 3g;
(2), prepare aqueous polyurethane grafted emulsion: in another container, add PCDL respectively, the mixture of isophorone diisocyanate and diphenylmethanediisocyanate places 75 ℃ oil bath to react 2h to sufficient reacting in this container then; Be cooled to 40 ℃ then; Add dimethylolpropionic acid reaction 1h, be warmed up to 80 ℃, add 1; 4-butyleneglycol insulation reaction 1h obtains base polyurethane prepolymer for use as;
Base polyurethane prepolymer for use as is cooled to 40 ℃, in container, adds the nano-TiO of step (1) preparation
2Dispersion liquid stirs 0.5h in 40 ℃ of oil baths, add triethylamine again and carry out neutralization reaction 0.5h, obtains midbody;
Under high-speed stirring, deionized water is slowly joined in the midbody in 0.5h, it is subsequent use to obtain aqueous polyurethane grafted emulsion;
The usage ratio of the used component of this step is following weight part: 20 parts of polycarbonate diols, 1 ~ 5 part of isophorone diisocyanate, 9 ~ 15 parts of diphenylmethanediisocyanates; 1.5 ~ 2.5 parts of dimethylolpropionic acids; 1,0.5 ~ 2.5 part of 4-butyleneglycol, 1.0 ~ 2.0 parts of triethylamines; 40 ~ 70 parts of deionized waters, TiO in per 100 parts of solids contents
2Account for 2 ~ 4 parts;
(3), the preparation of stain resistant aqueous polyurethane material: with four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 2-(2-hydroxyl-3,5-two fourth uncles base phenyl)-5-chlorinated benzotriazole is mixed to join in the aqueous polyurethane grafted emulsion that step (2) obtains;
Weight with aqueous polyurethane grafted emulsion is radix; Four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] the pentaerythritol ester addition is 0.05% ~ 0.1%, (2-hydroxyl-3,5-two fourth uncles base phenyl)-5-chlorinated benzotriazole add-on is 0.1 ~ 0.3% to 2-.
Described dispersion agent is one or more mixtures according to arbitrary proportion in X 2073, polyoxyethylene glycol-1000, polyoxyethylene glycol-1500, polyoxyethylene glycol-2000, the Sodium hexametaphosphate 99.
Described N, dinethylformamide purity>=99.5% is with H
+Meter acidity is 0.1mmol/100g, and moisture content is lower than 1%.
Described nano-powder TiO
2Be rutile-type, purity>=99.9%, particle diameter are 25 ~ 50nm.
Described polycarbonate diol is obtained by the alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of carbonatoms 4～12.
The average molecular mass Mn of described polycarbonate diol is 1000～2000 g/mol.
Positively effect of the present invention is:
The anti-yellowing property that how to improve aromatic waterborne polyurethane is attracting the concern of numerous researchers all the time, wherein aspect nano-material modified, has obtained more achievement.Because nano-particles size is little, specific surface area is big, can produce quantum effect and surface effects, make the more conventional matrix material of nano composite material have more excellent physicals and mechanical property.Adopt suitable method with inorganic nano-particle, carbon nanotube or nano imvite lamella and aqueous polyurethane carry out compound, and the over-all properties of prepared matrix material can obtain very big improvement, has expanded its Application Areas, has improved its result of use.People such as Chen Jiahua point out that the nanometer coating and decorating material can improve the anti-xanthochromia and the ageing-resistant performance of coatings, and wear resistance, water-repellancy, heat-resisting winter hardiness etc. make coating have self-cleaning preferably and sterilizing ability simultaneously, also can improve the opacifying power of coating.
Nano-TiO
2Electronic structure, exist by valence band that is full of electronics and the conduction band structure that do not have the unoccupied orbital of electronics to form and to forbid band gap.Work as TiO
2Receive rayed, the big photoabsorption of band gap energy that is under an embargo, the electron excitation of valence band is to conduction band.Because TiO
2The band gap of forbidding be about 2.3eV, be equivalent to the luminous energy of about 410nm wavelength.So TiO
2Electronics can receive the ultraviolet excitation of wavelength less than 410nm, thereby form the ability of good scattering and absorbing ultraviolet light, join in the aqueous polyurethane, can reach fabulous anti-xanthochromia effect.
Specifically, positively effect of the present invention is:
(1), the present invention adopts the adding nano-TiO
2In conjunction with adding antioxidant 1010 and UV light absorber UV-327 is compound changes
The property agent mode to have obtained anti-xanthochromia grade be 4 ~ 4.5 aromatic copolycarbonate type aqueous polyurethane emulsion, play great role for the use field that enlarges light-coloured coating.
(2), adopt MDI and IPDI carried out composite and polycarbonate diol reaction to reduce the level of response of MDI, get
To the higher aqueous polyurethane emulsion of stability.
(3), the mode with powder synthetic (promptly before emulsification, adding) adds nano-TiO
2, overcome the simple mechanical blend and made
The mechanical stability that becomes is poor, the problem of inorganic materials and organic phase consistency difference.
Description of drawings
Fig. 1 is instance 1 the first step nano-TiO
2The transmission electron microscope picture of dispersion liquid, 200,000 times of magnifications.
Fig. 2 is the nano-TiO of instance 1 preparation
2The transmission electron microscope picture of modified aqueous polyurethane emulsion, 200,000 times of magnifications.
Embodiment
Below in conjunction with the practical implementation method, further specify the present invention.
Embodiment 1
The first step: nano-TiO
2The preparation of dispersion liquid
In container, add 0.300g Sodium hexametaphosphate 99 and 30mlN, dinethylformamide, and dispersion agent is dissolved fully, add 3.000g nano-powder TiO then
2, in ultrasonic cell disruptor, sonicated 30min obtains nano-TiO under the 540w
2Dispersion liquid is subsequent use.Described nano-powder TiO
2Be rutile-type, purity>=99.9%, particle diameter are 25nm ~ 50nm.As can be seen from Figure 1 nano-TiO
2In DMF solution, has good dispersiveness.
Second step: prepare aqueous polyurethane grafted emulsion.
In another container, add the 20.000g PCDL respectively, the mixture of 1.095g isophorone diisocyanate and 9.857g diphenylmethanediisocyanate places 75 ℃ oil bath reaction 2h to sufficient reacting, to be cooled to 40 ℃ in this container then; Add the 1.557g dimethylolpropionic acid, reaction 1h is warmed up to 80 ℃; Add 1.354g 1; The 4-butyleneglycol, insulation reaction 1h obtains base polyurethane prepolymer for use as.Base polyurethane prepolymer for use as is cooled to 40 ℃, in container, adds the nano-TiO of 6.600g step (1) preparation
2Dispersion liquid stirs 0.5h in 40 ℃ of oil baths, add the 1.010g triethylamine again and carry out neutralization reaction 0.5h, obtains midbody; Deionized water with 41.156g under high-speed stirring slowly joins in the midbody, about 0.5h of joining day, and it is subsequent use to obtain aqueous polyurethane grafted emulsion; As can beappreciated from fig. 2 nano-TiO
2In polyaminoester emulsion, well disperseed.Said polycarbonate diol is obtained by the alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of carbonatoms 4～12, and average molecular mass Mn is 1000～2000 g/mol.
The 3rd step: the preparation of the aromatic copolycarbonate of anti-xanthochromia type water-base polyurethane material: 0.0306g antioxidant 1010 and 0.0612g UV light absorber UV-327 are mixed to join in the aqueous polyurethane grafted emulsion that step (2) obtains.
Emulsion PCU-03 finish that instance 1 is obtained and homemade waterborne, polycarbonate type polyurethane resin (PCU-01), homemade interpolation nano-TiO
2The PCU that the powder blend obtains (PCU-02) covers with paint, lacquer, colour wash, etc. according to the covering with paint prescription in the table 1.After treating leather appearance drying, cut two on the sample of 30 * 40mm, a slice wherein is placed in the non-yellowing test case that is heated to 50 ℃ in advance, at ultra violet lamp held 24h, another test piece is positioned in the climatic chamber, does the usefulness of contrast.The arrival specified time is promptly taken out test piece, places cooling 10min under the normal temperature condition, on the grey colour atla, contrasts colour-change with former print and obtains the xanthochromia result, like table 2.Can find out that by table 2 three kinds of leather appearance behind ultra violet lamp all have the xanthochromia phenomenon, but not add nano-TiO
2Polycarbonate type aqueous polyurethane (PCU-01) xanthochromia effect more serious, the xanthochromia grade is between 2.5 ~ 3.Add 3% nano-TiO by contrast
2The modified polycarbonate type aqueous polyurethane xanthochromia degree that obtains will reduce by 0.5 grade, and with nano-TiO
2Adopt the mode xanthochromia degree that adds in the building-up process also to reduce greatly, improved 1 ~ 1.5 grade.
Table 1 is covered with paint, lacquer, colour wash, etc. prescription
Table 2 coating xanthochromia test result
| Leather appearance numbering | Standard class | The actual measurement grade |
| 1# | 5 | 2．5~3 |
| 2# | 5 | 3~3．5 |
| 3# | 5 | 4．5 |
Annotate: 1 ~ 3# appearance is respectively the leather appearance after PCU-01 finish, PCU-02 finish, two coverings with paint of PCU-03 finish utilization prescription, and the result is that three kinds of samples are through ultra violet lamp 24 xanthochromia change of rank as a child in the table.
Embodiment 2
The first step: nano-TiO
2The preparation of dispersion liquid
In container, add 0.150g polyoxyethylene glycol-4000 and 30mlN respectively, dinethylformamide, and dispersion agent is dissolved fully, add 3.000g nano-powder TiO then
2, in ultrasonic cell disruptor, sonicated 30min obtains nano-TiO under the 540w
2Dispersion liquid is subsequent use; Described nano-powder TiO
2Be rutile-type, purity>=99.9%, particle diameter are 40nm.
Second step: the preparation of polycarbonate type aqueous polyurethane emulsion.
In another container, add the 20.000g PCDL respectively, the mixture of 0.690g isophorone diisocyanate and 6.210g diphenylmethanediisocyanate places 75 ℃ oil bath reaction 2h to sufficient reacting, to be cooled to 40 ℃; Add 1.883 g dimethylolpropionic acids (; Reaction 1h is warmed up to 80 ℃, adds 0.154g 1; 4-butyleneglycol insulation reaction 1h obtains base polyurethane prepolymer for use as; Base polyurethane prepolymer for use as is cooled to 40 ℃, in container, adds the nano-TiO of 10.912g step (1) preparation
2Dispersion liquid stirs 0.5h in 40 ℃ of oil baths, add the 1.350g triethylamine again and carry out neutralization reaction 0.5h and obtain midbody; Deionized water with 53.919g under high-speed stirring slowly joins about 0.5h of joining day in the midbody, and it is subsequent use to obtain aqueous polyurethane grafted emulsion; The alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of said polycarbonate diol cause carbonatoms 4～12 obtain, and average molecular mass Mn is 1000～2000 g/mol.
The 3rd step: the preparation of the aromatic copolycarbonate of anti-xanthochromia type water-base polyurethane material: 0.0101g antioxidant 1010 and 0.0204g UV light absorber UV-327 are mixed to join in the polyaminoester emulsion that step (2) obtains.
Embodiment 3
The first step: nano-TiO
2The preparation of dispersion liquid
In container, add respectively the 0.210g X 2073 in and 30mlN, dinethylformamide, and dispersion agent is dissolved fully adds 3.000g nano-powder TiO then
2, in ultrasonic cell disruptor, sonicated 30min obtains nano-TiO under the 540w
2Described nano-powder TiO
2Be rutile-type, purity>=99.9%, particle diameter are 50nm.
Second step: the preparation of polycarbonate type aqueous polyurethane emulsion.
In another container, add the 20.000g PCDL respectively, the mixture of 2.903g isophorone diisocyanate and 11.612g diphenylmethanediisocyanate places 75 ℃ oil bath reaction 2h to sufficient reacting, to be cooled to 40 ℃ in this container then; Add 2.071 g dimethylolpropionic acids, reaction 1h is warmed up to 80 ℃; Add 1.672g 1; The 4-butyleneglycol, insulation reaction 1h obtains base polyurethane prepolymer for use as; , base polyurethane prepolymer for use as is cooled to 40 ℃, in container, add the nano-TiO of 15.927g step (1) preparation
2Dispersion liquid stirs 0.5h in 40 ℃ of oil baths, add 1.485 g triethylamines again and carry out neutralization reaction 0.5h and obtain midbody.Deionized water with 129.082g under high-speed stirring slowly joins in the midbody in 0.5h, and it is subsequent use to obtain aqueous polyurethane grafted emulsion; The alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of said polycarbonate diol cause carbonatoms 4～12 obtain, and average molecular mass Mn is 1000～2000 g/mol.
The 3rd step: the preparation of the aromatic copolycarbonate of anti-xanthochromia type water-base polyurethane material: join in the polyaminoester emulsion that step (2) obtains 0.067g antioxidant 1010 and 0.133 g UV light absorber UV-327 are compound.
Among the present invention, DMF is meant N, dinethylformamide.Antioxidant 1010 is meant four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.UV light absorber UV-327 is meant 2-(2-hydroxyl-3,5-two fourth uncles base phenyl)-5-chlorinated benzotriazole.
Claims (6)
1. the preparation method of a stain resistant aqueous polyurethane material is characterized in that preparation process is following:
(1), preparation nano-TiO
2Dispersion liquid: in container, add dispersion agent and N respectively, dinethylformamide, and dispersion agent is dissolved fully, add nano-powder TiO then
2, in ultrasonic cell disruptor, sonicated 30min obtains nano-TiO under the 540w
2Dispersion liquid is subsequent use;
Wherein every 100mlN adds nano-powder TiO in the dinethylformamide
25 ~ 10g, dispersion agent 1.5 ~ 3g;
(2), prepare aqueous polyurethane grafted emulsion: in another container, add PCDL respectively, the mixture of isophorone diisocyanate and diphenylmethanediisocyanate places 75 ℃ oil bath to react 2h to sufficient reacting in this container then; Be cooled to 40 ℃ then; Add dimethylolpropionic acid reaction 1h, be warmed up to 80 ℃, add 1; 4-butyleneglycol insulation reaction 1h obtains base polyurethane prepolymer for use as;
Base polyurethane prepolymer for use as is cooled to 40 ℃, in container, adds the nano-TiO of step (1) preparation
2Dispersion liquid stirs 0.5h in 40 ℃ of oil baths, add triethylamine again and carry out neutralization reaction 0.5h, obtains midbody;
Under high-speed stirring, deionized water is slowly joined in the midbody in 0.5h, it is subsequent use to obtain aqueous polyurethane grafted emulsion;
The usage ratio of the used component of this step is following weight part: 20 parts of polycarbonate diols, 1 ~ 5 part of isophorone diisocyanate, 9 ~ 15 parts of diphenylmethanediisocyanates; 1.5 ~ 2.5 parts of dimethylolpropionic acids; 1,0.5 ~ 2.5 part of 4-butyleneglycol, 1.0 ~ 2.0 parts of triethylamines; 40 ~ 70 parts of deionized waters, TiO in per 100 parts of solids contents
2Account for 2 ~ 4 parts;
(3), the preparation of stain resistant aqueous polyurethane material: with four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 2-(2-hydroxyl-3,5-two fourth uncles base phenyl)-5-chlorinated benzotriazole is mixed to join in the aqueous polyurethane grafted emulsion that step (2) obtains;
Weight with aqueous polyurethane grafted emulsion is radix; Four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] the pentaerythritol ester addition is 0.05% ~ 0.1%, (2-hydroxyl-3,5-two fourth uncles base phenyl)-5-chlorinated benzotriazole add-on is 0.1 ~ 0.3% to 2-.
2. the preparation method of stain resistant aqueous polyurethane material according to claim 1, it is characterized in that: dispersion agent is one or more mixtures according to arbitrary proportion in X 2073, polyoxyethylene glycol-1000, polyoxyethylene glycol-1500, polyoxyethylene glycol-2000, the Sodium hexametaphosphate 99.
3. the preparation method of stain resistant aqueous polyurethane material according to claim 1, it is characterized in that: N, dinethylformamide purity>=99.5% is with H
+Meter acidity is 0.1mmol/100g, and moisture content is lower than 1%.
4. the preparation method of stain resistant aqueous polyurethane material according to claim 1 is characterized in that: nano-powder TiO
2Be rutile-type, purity>=99.9%, particle diameter are 25 ~ 50nm.
5. the preparation method of stain resistant aqueous polyurethane material according to claim 1, it is characterized in that: described polycarbonate diol is obtained by the alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of carbonatoms 4～12.
6. the preparation method of stain resistant aqueous polyurethane material according to claim 2, it is characterized in that: the average molecular mass Mn of described polycarbonate diol is 1000～2000 g/mol.
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Cited By (9)
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| CN102924901A (en) * | 2012-11-27 | 2013-02-13 | 山东全杰皮革研究所有限公司 | Preparation method of light-resistant MDI (diphenyl-methane-diisocyanate) polyurethane |
| CN103073696A (en) * | 2013-01-30 | 2013-05-01 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
| CN103725182A (en) * | 2013-12-11 | 2014-04-16 | 上海嘉宝莉涂料有限公司 | Preparation method for yellowing resistant aromatic polycarbonate type waterborne polyurethane coating material |
| CN105566594A (en) * | 2016-01-29 | 2016-05-11 | 佛山市聚成生化技术研发有限公司 | Preparation method of cow leather coating agent containing polyurethane and prepared cow leather coating agent |
| CN106046307A (en) * | 2016-07-14 | 2016-10-26 | 安徽亳州喜宝鞋服有限公司 | Yellowing-resisting polyurethane composite for shoe materials and preparation method of polyurethane composite |
| CN107540806A (en) * | 2016-06-29 | 2018-01-05 | 台湾永光化学工业股份有限公司 | Polyurethane type high molecular ultraviolet absorbent |
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| CN102924901A (en) * | 2012-11-27 | 2013-02-13 | 山东全杰皮革研究所有限公司 | Preparation method of light-resistant MDI (diphenyl-methane-diisocyanate) polyurethane |
| CN102924901B (en) * | 2012-11-27 | 2014-07-23 | 山东全杰皮革研究所有限公司 | Preparation method of light-resistant MDI (diphenyl-methane-diisocyanate) polyurethane |
| CN103073696A (en) * | 2013-01-30 | 2013-05-01 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
| CN103073696B (en) * | 2013-01-30 | 2014-08-13 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
| CN103725182A (en) * | 2013-12-11 | 2014-04-16 | 上海嘉宝莉涂料有限公司 | Preparation method for yellowing resistant aromatic polycarbonate type waterborne polyurethane coating material |
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| CN106046307A (en) * | 2016-07-14 | 2016-10-26 | 安徽亳州喜宝鞋服有限公司 | Yellowing-resisting polyurethane composite for shoe materials and preparation method of polyurethane composite |
| CN108309168A (en) * | 2017-12-31 | 2018-07-24 | 广州海鑫无纺布实业有限公司 | A kind of preparation method of high-durability frosted cleaning cloth |
| CN108342833A (en) * | 2017-12-31 | 2018-07-31 | 广州海鑫无纺布实业有限公司 | A kind of preparation method of the high-hydroscopicity silk fiber non-woven fabrics of color inhibition |
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